Iron(III) complexes with N 4- para -tolyl-thiosemicarbazones: spectral and electrochemical studies and toxicity to Artemia salina

Iron(III) complexes [Fe(H2Fo4pT)Cl₃] (1), [Fe(H2Ac4pT)Cl₃] (2) and [Fe(H2Bz4pT)Cl₃] (3) with N⁴ -para-tolyl-thiosemicarbazones derived from 2-formyl (H2Fo4pT), 2-acetyl (H2Ac4pT) and 2-benzoylpyridine (H2Bz4pT) were prepared and characterized. EPR data for 1–3 reveal the presence of low-spin iron(III) with d _xz ²d _yz ²d _xy ¹ ground state. Electrochemical studies of the complexes showed mostly metal-centered redox changes with a quasi-reversible Fe(III)/Fe(II) couple. H2Fo4pT and H2Ac4pT exhibited toxicity against Artemia salina at low doses (LD₅₀ = 27.5 µM and LD₅₀ = 4.7 µM, respectively). Upon coordination the toxicity increased substantially in the case of [Fe(H2Fo4pT)Cl₃] (LD₅₀ = 1.9 µM) and did not change for [Fe(H2Ac4pT)Cl₃]. H2Bz4pT and its iron(III) complex were not soluble in water.     

Copolymerization of 4‐Propanoylphenyl Acrylate with Methyl Methacrylate: Synthesis,Characterization and Reactivity Ratios

The new acrylic monomer 4‐propanoylphenyl acrylate (PPA) was synthesized and copolymerized with methyl methacrylate (MMA) in methyl ethyl ketone at 70±1°C using benzoyl peroxide as a free radical initiator. The copolymers were characterized by FT‐IR, ¹H‐NMR and ¹³C‐NMR spectroscopic techniques. The compositions of the copolymers were determined by ¹H‐NMR analysis. The reactivity ratios of the monomers were determined using Fineman‐Ross (r₁=0.5535 and r₂=1.5428), Kelen‐Tüdös (r₁=0.5307 and r₂=1.4482), and Ext. Kelen‐Tüdös (r₁=0.5044 and r₂=1.4614), as well as by a nonlinear error‐in‐variables model (EVM) method using a computer program, RREVM (r₁=0.5314 and r₂=1.4530). The solubility of the polymers was tested in various polar and non‐polar solvents. The elemental analysis was determined by a Perkin‐Elmer C‐H analyzer. The molecular weights (M_w and M_n) of the copolymers were determined by gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of MMA in the copolymers. Glass transition temperatures of the copolymers were found to increase with an increase in the mole fraction of MMA in the copolymers.     

Synthesis and bulk characterization of new P(CB‐b‐S) diblock copolymers

Strongly asymmetric chlorinated polybutadiene‐b‐polystyrene, [P((CB)_x‐b‐(PS)_y)] diblock copolymers with increasing x/(x + y) ratios (up to 5.2 mol %) have been synthesized by the selective chlorination of the polybutadiene (PB) block in solution. Chlorination has been performed in anhydrous dichloromethane added with an antioxidant [2,2′‐methylenebis‐(6‐tert‐butyl‐4‐methyl‐phenol)], at −50°C, under a continuous Ar flow and in the dark. Under the optimized experimental conditions, the PB chlorination is not complete, but the PS block is left unmodified. Even in the presence of a large chlorine excess (Cl₂/butene unit molar ratio of 2.5), the experimental degree of chlorination of homo PB does not exceed 85%. The chlorinated copolymers have been characterized by ¹H‐NMR, IR spectroscopy, size‐exclusion chromatography, and elemental analysis. The chlorinated copolymers have also been studied by DSC and SAXS after annealing at 150°C. Although at this temperature the parent homopolymers are immiscible, no microphase separation has been observed for the block copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 233–244, 1999     

Crystal structure and spectroscopic behavior of three new tris-oxalatoferrate(III) salts

A new general synthetic procedure for preparation of Na₃[Fe(C₂O₄)₃]·5H₂O (1), Rb₃[Fe(C₂O₄)₃]·3H₂O (2), and Cs₃[Fe(C₂O₄)₃]·2H₂O (3) was developed. The crystal structures of these salts have been determined by single crystal X-ray diffraction. Salt 1 crystallizes in the monoclinic space group C2/c with Z = 8, salt 2 in P2₁/c with Z = 4, and salt 3 in P2₁/n with Z = 4. The three new salts and K₃[Fe(C₂O₄)₃]·3H₂O, prepared for comparative purposes, were further characterized by infrared and ⁵⁷Fe-Mössbauer spectroscopy. These spectra are discussed in comparison with those of related oxalato complexes.     

Synthesis and characterization of model diblock copolymers of poly(dimethylsiloxane) with poly(1,4‐butadiene) or poly(ethylene)

Model diblock copolymers of poly(1,4‐butadiene) (PB) and poly(dimethylsiloxane) (PDMS), PB‐b‐PDMS, were synthesized by the sequential anionic polymerization (high vacuum techniques) of butadiene and hexamethylciclotrisiloxane (D₃) in the presence of sec‐BuLi. By homogeneous hydrogenation of PB‐b‐PDMS, the corresponding poly(ethylene) and poly(dimethylsiloxane) block copolymers, PE‐b‐PDMS, were obtained. The synthesized block copolymers were characterized by nuclear magnetic resonance (¹H and ¹³C NMR), size‐exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and rheology. SEC combined with ¹H NMR analysis indicates that the polydispersity index of the samples (M_w/M_n) is low, and that the chemical composition of the copolymers varies from low to medium PDMS content. According to DSC and TGA experiments, the thermal stability of these block copolymers depends on the PDMS content, whereas TEM analysis reveals ordered arrangements of the microphases. The morphologies observed vary from spherical and cylindrical to lamellar domains. This ordered state (even at high temperatures) was further confirmed by small‐amplitude oscillatory shear flow tests. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1579–1590, 2006     

Stereospecific sequential block copolymerizations of styrene and 1,3‐butadiene with a C5Me5TiMe3/B(C6F5)3/Al(oct)3 catalyst

This article reports a new methodology for preparing highly stereoregular styrene (ST)/1,3‐butadiene (BD) block copolymers, composed of syndiotactic polystyrene (syn‐PS) segments chemically bonded with cis‐polybutadiene (cis‐PB) segments, through a stereospecific sequential block copolymerization of ST with BD in the presence of a C₅Me₅TiMe₃/B(C₆F₅)₃/Al(oct)₃ catalyst. The first polymerization step, conducted in toluene at ?25 °C, was attributed to the syndiospecific living polymerization of ST. The second step, conducted at ?40 °C, was attributed to the cis‐specific living polymerization of BD. The livingness of the whole polymerization system was confirmed through a linear increase in the weight‐average molecular weights of the copolymers versus the polymer yields in both steps, whereas the molar mass distributions remained constant. The profound cross reactivity of the styrenic‐end‐group active species with BD toward ST led to the production of syn‐PS‐b‐cis‐PB copolymers with extremely high block efficiencies. Because of the presence of crystallizable syn‐PS segments, this copolymer exhibited high melting temperatures (up to 270 °C), which were remarkably different from those of the corresponding anionic ST–BD copolymers, for which no melting temperatures were observed. Scanning electron microscopy pictures of a binary syn‐PS/cis‐PB blend with or without the addition of the syn‐PS‐b‐cis‐PB copolymers proved that it could be used as an effective compatibilizer for noncompatibilized syn‐PS/cis‐PB binary blends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1188–1195, 2005     

Copolymerization of N-allenylimidazole with di(ethylene glycol) divinyl ether and complexation of the copolymers with CuCl2

Polyfunctionalized linear copolymers of N-allenylimidazole and di(ethylene glycol) divinyl ether with polyconjugated (polyvinylene) blocks in the main chain and exomethylene bonds and vinyloxyethoxyethyl groups in the side chain were prepared. Using the reaction of the copolymers with CuCl₂, a possibility of synthesis of polymeric metal complexes for catalysis of organic reactions was shown. The IR and ESR spectra of the complexes were studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 973–977, June, 2006.     

Complexation and thermogravimetric investigation on tin(II) and tin(IV) with norfloxacin as antibacterial agent

The interaction of tin(II) and tin(IV) chlorides with norfloxacin (NOR) has been investigated. Elemental analysis, infrared, mass spectra and thermal analysis have been used to characterize the isolated solid complexes. The results support the formation of complexes with the formula [Sn(NOR)₂]Cl₂·4H₂O and [Sn(NOR)₃]Cl₄. The infrared spectra of the isolated solid complexes suggested that NOR act as bidentate ligand through the carbonyl oxygen atom and one oxygen atom of the carboxylic group forming six-membered rings with the tin ions. The interpretation, mathematical analysis and evaluation of kinetic parameters of thermogravimetric (TGA) and its differential (DTG), such as entropy of activation, pre-exponential factors, activation energy evaluated by using Coats–Redfern and Horowitz–Metzger equations are carried out for two complexes. The data obtained indicate that the two complexes decompose in one stage and general mechanisms describing the decomposition are suggested. Furthermore, the electronic, and ¹H?NMR spectra have been studied.     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Interaction of organolead(IV) derivatives with formyl- and acetylferrocene thiosemicarbazones: Coordination versus dephenylation or reductive elimination processes

The reaction of Ph₂PbCl₂ with formylferrocene and acetylferrocene thiosemicarbazones (HTSCs) in methanol afforded the corresponding adduct [Ph₂PbCl₂(HTSC)₂] or, in one case, the complex [Ph₂PbCl(TSC)]. X-ray crystallography of four of the adducts showed them to be all-trans octahedral complexes with the HTSC ligand S-bound to the metal. The IR spectrum of [Ph₂PbCl(TSC)] suggests that the TSC⁻ ligand is N,S-coordinated. The reaction of Ph₂Pb(OAc)₂ with HTSCs in methanol gave either [Ph₂Pb(OAc)₂(HTSC)₂] or [Ph₂Pb(OAc)(TSC)], which was also obtained from Ph₃Pb(OAc) via a spontaneous dephenylation process. In the former complexes the HTSC ligand is S-coordinated in the solid state. X-ray crystallography of two of the four [Ph₂Pb(OAc)(TSC)] complexes showed that the thiosemicarbazonate anion is N,S-coordinated and the acetate is anisobidentate. Cyclic voltammetry of one [Ph₂PbCl₂(HTSC)₂] adduct and the corresponding [Ph₂Pb(OAc)(TSC)] complex showed that the inductive effect of coordination to lead is transmitted to the ferrocenyl group. Surprisingly, the reaction of Me₂Pb(OAc)₂ with HTSCs afforded only [Pb(TSC)₂] complexes, possibly via redistribution and reductive elimination processes.     

Synthesis and spectroscopic study of hexadecaalkyl-substituted rare-earth diphthalocyanines

New hexadecaalkyl-substituted diphthalocyanine complexes of lanthanides ^RPc₂Ln (R = Et, or Bu; Ln = Lu, Dy, or Eu) were synthesized by three methods: in solution in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, in a melt of a mixture of the reagents, and under microwave irradiation. The first of the above-mentioned procedures has an advantage for the preparation of Dy and Eu diphthalocyanines, whereas the melt synthesis is a method of choice for the preparation of Lu complexes. The reaction time decreases in going from the first to the third method. The structures of the complexes were confirmed by mass spectrometry, NMR spectroscopy, and electronic absorption spectroscopy.     

顺磁性镧系金属有机配合物的1H核磁共振研究

顺磁类的核磁共振研究大多是简单化合物,偏重理论方面的研究,对镧系配合物曾有报道。由于这类样品对空气和湿气极为敏感,在国内外研究顺磁性¹H谱甚少。本文研究了含氯桥的醚基取代环戊二烯镧系配合物二聚体的¹H化学位移,线宽,弛豫时间T₁和磁化率,从中找出了顺磁类有机镧系配合物¹H NMR的规律。     

Copolymers of 4‐(3′,4′‐Dimethoxycinnamoyl)phenyl Acrylate and MMA: Synthesis,Characterization, Photocrosslinking Properties,and Monomer Reactivity Ratios

Abstract

4‐(3′,4′‐Dimethoxycinnamoyl)phenyl acrylate (DMCPA) containing pendant chalcone moiety was copolymerized with methyl methacrylate (MMA) by radical polymerization in ethyl methyl ketone at 70°C under a nitrogen atmosphere using benzoyl peroxide (BPO) as a free radical initiator. The prepared polymer was characterized by UV, FT‐IR, ¹H‐NMR, and ¹³C‐NMR spectra. The composition of the copolymer was determined using ¹H‐NMR analysis. The monomer reactivity ratios of copolymerization were determined using conventional linearization methods such as Fineman–Ross (r ₁ = 0.26 and r ₂ = 0.61), Kelen–Tudos (r ₁ = 0.26 and r ₂ = 0.61), and Ext. Kelen–Tudos (r ₁ = 0.23 and r ₂ = 0.59), and a non‐linear error‐in‐variables model (EVM) method using the computer program RREVM (r ₁ = 0.2541 and r ₂ = 0.6094). The molecular weights (M _w and M _n) of the copolymers were determined by gel permeation chromatography. Thermogravimetric analysis of the polymers in air reveals that the stability of the copolymers decreases with an increase in the mole fraction of MMA in the copolymers. The solubility of the polymers was tested in various polar and non‐polar solvents. The glass transition temperature of the copolymers was determined as a function of copolymer composition. The copolymers were sensitive to UV light and became crosslinked after irradiation with 254 nm light.     

Formation and structure of diruthenium complexes Ru2(CO)6−n (PPh3) n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2)

Ruthenium carbonyl triphenylphosphine complexes Ru₂(CO)_6−n (PPh₃) _n {μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} (n=1, 2) were obtained by the reaction of complex Ru₂(CO)₆{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh₃ in refluxing toluene. The complexes were characterized by IR and by¹H,¹³C, and³¹P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation of the Ru₃(CO)₈(PPh₃){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh₃ ligand at the ruthenium atom of the ruthenacyclopentadiene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1843, September, 1998     

Mononuclear,homo- and hetero-binuclear complexes of 1-(5-(1-(2-aminophenylimino)ethyl)-2,4-dihydroxyphenyl)ethanone: synthesis,magnetic, spectral,antimicrobial, antioxidant,and antitumor studies

A new Schiff base, H₂L, was prepared by condensation of 4,6-diacetylresorcinol with o-phenylenediamine in molar ratio 1?:?1. The ligand reacted with copper(II), nickel(II), cobalt(II), iron(III), zinc(II), oxovanadium(IV), and dioxouranium(VI) ions in the absence and presence of LiOH to yield mononuclear and homobinuclear complexes. The mononuclear dioxouranium(VI) complex [(HL)-(UO₂)(OAc)(H₂O)]·5H₂O was used to synthesize heterobinuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, ¹H-, and ¹³C-NMR, electronic, ESR and mass spectra, conductivity, and magnetic susceptibility measurements as well as thermal analysis. In the absence of LiOH, mononuclear complexes (1, 4, and 9) were obtained; in the presence of LiOH, binuclear complexes (3, 5, 7, and 10) as well as mononuclear complexes (2, 6, and 8) were obtained. In the mononuclear complexes, the coordinating sites are the phenolic oxygen, azomethine nitrogen, and amino nitrogen. In addition to these coordinating sites, the free carbonyl and phenolic OH are involved in coordination in binuclear complexes. The metal complexes exhibited octahedral, tetrahedral, and square planar geometries while the uranium is seven-coordinate. The antimicrobial and antioxidant activities of the ligand and its complexes were investigated. The ligand and the metal complexes showed antitumor activity against Ehrlich Acites Carcinoma.     

TRANSITION METAL COMPLEXES OF AMINOPHOSPHONIC ACID ANALOGUES OF METHIONINE AND ALANINE IN AQUEOUS SOLUTION

Abstract

The stoichiometrics and stability constants of the nickel(II), copper(II) and zinc(II) complexes of l-amino-3-methylthiopropanephosphonic acid (MetP) and 1-amino-ethanephosphonic acid (a-AlaP) have been determined pH-metrically at 25°C at an ionic strength of 0.2 mol dm^?3 (KC1). From the stability data and the absorption spectra of the complexes it has been established that simple aminophosphonic acids coordinate to the nickel(II) and copper(II) ions forming chelate complexes in which the metal binding mode is bidentate with the {NH₂, PO₃ ^2-} donor set. ³¹P and ¹H NMR measurements showed that MetP and α-AlaP exhibit similar properties in the presence of zinc(II) ions, but the ligand reacts to form a cyclic phosphonoamidate in neutral and slightly alkaline solution in the Zn(II)-α-AlaP system and at slightly acidic conditions in the Zn(II)-MetP system. This difference reveals that the latter ligand at pH > 7 prefers Zn(II) coordination involving all possible (amino, phosphonate and thioether sulfur) donor groups.     

Preparation and characterization of spherical PP/PB alloys with MgCl2-supported Ziegler-Natta catalyst

Polypropylene（PP）/polybutene-1（PB） alloys within reactor were prepared by MgCl₂-supported Ziegler-Natta catalyst with sequential two-stage polymerization technology.First,propylene homo-polymerizations were carried out to form isotactic polypropylene（iPP） particles containing active catalyst.Then,butene-1 was subsequently polymerized to form polybutene-1 phase inside the iPP particles.Finally,iPP/PB alloys with spherical shape and adjustable PB content were synthesized.The catalytic activity and catalytic stereospecificity of the Z-N catalyst in the two-stage polymerization process are discussed.The composition and physical properties of the PP alloys were characterized by FT-IR,¹³C-NMR,SEM,DSC and XRD.It was found that the in-reactor PP alloys are mainly composed of PP and PB with a little amount of poly（butene-co -propylene） random copolymers and poly（butene-block-propylene） block copolymers.SEM measurements verified that the PB phases with size in the range of 300-400 nm dispersed in the PP matrix uniformly.The incorporation of PB upon the PP matrix affects the properties of final products greatly.     

Cr,Co, and Mn arene π-complexes based on diphenyl- and triphenylmethane

The interaction of Ph₂CH₂ and Ph₃CH with Cr(CO)₆, Co₂(CO)₈, and Mn(CO)₅BF₄ leads to mononuclear LCr(CO)₃, LCo₄(CO)₉, and [LMn(CO)₃]BF₄ π-arene complexes. Similarly, LCr(CO)₃Co₄(CO)₉ and [LCr(CO)₃Mn(CO)₃]BF₄ heteroaromatic derivatives are obtained from LCr(CO)₃ complexes, whereas LCo₄(CO)₉ complexes afford L[Co₄(CO)₉]₂ bicluster derivatives. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1809–1812, October, 1993.     

Selective synthesis and spectroscopic properties of alkyl-substituted lanthanide(<Emphasis Type="SmallCaps">III</Emphasis>) mono-, di-, and triphthalocyanines

Methods for the selective synthesis of mono-(^RPcLnOAc), di-(^RPc₂Ln), and triphthalocyanines (^RPc₃Ln₂) of rare-earth metals (Ln = Lu, Er, Eu) from symmetrically substituted 2,3,9,10,16,17,23,24-octaalkylphthalocyanines ^RPcH₂ (R = Et, Bu) were developed. The synthesized complexes were characterized by NMR spectroscopy, mass spectrometry, and electronic absorption spectra. The conditions for ¹H NMR spectra recording were optimized. Regularities in changing the spectral properties of the synthesized compounds, depending on the lanthanide nature and the planarity of metal phthalocyanine complexes, were found. tom@org.chem.msu.su Dedicated to Academician A. L. Buchachenko on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2024–2030, September, 2005.     

Complexes derived from some biologically active ligands

Complexes derived from ampicillin (L1) and amoxicillin (L2) with (Mg(II), Ca(II), Zn(II), Cu(II), Ni(II), Co(II), Ce(III), Nd(III), UO₂(VI), Th(IV)) were prepared and characterized by elemental analysis, electrical conductivity measurements, magnetic susceptibility, IR, UV/Vis, and thermogravimetry. The formed complexes can be formulated as (ML(H₂O)₃(NO₃) _n ) except for Ce(III) which gave (CeL(H₂O)₃(Cl)₂). The ¹H NMR spectra of the Zn(II) complexes are compared to spectra of the ligands. The shift (δ) gave information about the chelating center of the ligands. The ligands and the synthesized complexes, derived from some alkali earth and transition metal ions, were tested as antibacterial reagents. The formed complexes had enhanced activity.